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| United States Patent |
5,260,435
|
|
Sawada
, et al.
|
November 9, 1993
|
Derivative of naphthalocyanine containing perfluoroalkyl group, process
for preparing the same and optical recording medium
Abstract
A derivative of naphthalocyanine containing a perfluoroalkyl group and
having a particular structure for ensuring excellent weather-proof
properties, extremely high solubility in various solvents and capability
of forming a film, and an optical recording medium prepared by using the
derivative and capable of recording while using a focused beam of a
semiconductor laser or the like. The derivative of naphthalocyanine
containing a perfluoroalkyl group may be prepared by reacting a
perfluoroalkanoyl peroxide having a particular structure with a
naphthalocyanine.
| Inventors:
|
Sawada; Hideo (Tsukuba, JP);
Mitani; Motohiro (Tsukuba, JP);
Nakayama; Masaharu (Tsuchiura, JP);
Morishita; Yoshii (Hitachi, JP);
Katayose; Mitsuo (Hitachi, JP);
Okamoto; Tadashi (Joyo, JP);
Hayashi; Nobuyuki (Hitachi, JP)
|
| Assignee:
|
Nippon Oil and Fats Co., Ltd. (Tokyo, JP);
Hitachi Chemical Co., Ltd. (Tokyo, JP)
|
| Appl. No.:
|
838781 |
| Filed:
|
March 18, 1992 |
| PCT Filed:
|
March 5, 1991
|
| PCT NO:
|
PCT/JP91/00292
|
| 371 Date:
|
March 18, 1992
|
| 102(e) Date:
|
March 18, 1992
|
| PCT PUB.NO.:
|
WO92/01689 |
| PCT PUB. Date:
|
February 6, 1992 |
Foreign Application Priority Data
| Jul 23, 1990[JP] | 2-192870 |
| Feb 21, 1991[JP] | 3-027401 |
| Feb 26, 1991[JP] | 3-031056 |
| Current U.S. Class: |
540/122; 540/128; 540/140 |
| Intern'l Class: |
C07B 047/30 |
| Field of Search: |
540/122,128,136,140
|
References Cited
| Foreign Patent Documents |
| 0277039 | Aug., 1988 | EP.
| |
| 61-186384 | Aug., 1986 | JP.
| |
Other References
CA:106: 166306m "Laser-Sensitive" optical recording medium (1987).
Hayashida et al., Chemistry Letters, The Chemistry Society of Japan, pp.
2137-2140, 1990.
Wheller et al., J. Am. Chem. Soc., 106:7404-7410, 1984.
Kovshev et al., Zh. Obshch. Khim., 42:696-699, 1972.
Firey et al., J. Am. Chem. Soc., 110:7626-7630, 1988.
|
Primary Examiner: Page; Thurman K.
Assistant Examiner: Venkat; Jyothsna
Attorney, Agent or Firm: Darby & Darby
Claims
We claim:
1. A derivative of naphthalocyanine containing a perfluoroalkyl group and
represented by the following formula (I) of;
##STR15##
wherein n.sub.1, n.sub.2, n.sub.3 and n.sub.4 each stand for an integer of
from 0 to 2, and n.sub.1 +n.sub.2 +n.sub.3 +n.sub.4 .noteq.0; and n.sub.5
stands for an integer of from 1 to 10.
2. A derivative of naphthalocyanine containing a perfluoroalkyl group and
represented by the following formula (II) of;
##STR16##
wherein M stands for (R).sub.3 SiO--Si--OSi(R).sub.3 or
[F(CF.sub.2).sub.n.sbsb.5 --(R).sub.2 SiO--Si--OSi(R).sub.3 where R is an
alkyl group having 1 to 10 carbon atoms; n.sub.1, n.sub.2, n.sub.3 and
n.sub.4 each stand for an integer of from 0 to 2 and n.sub.5 stands for an
integer of from 1 to 10, n.sub.1 +n.sub.2 +n.sub.3 +n.sub.4 .noteq.0 when
M is (R).sub.3 SiO--Si--OSi(R).sub.3.
Description
FIELD OF ART
The present invention relates to a novel derivative of naphthalocyanine
containing a perfluoroalkyl group, and particularly to a process for
preparing such an industrially useful derivative of naphthalocyanine
containing a perfluoroalkyl group and an optical recording medium capable
of recording information using a focused beam of a semiconductor laser.
BACKGROUND TECHNOLOGY
Cyanine compounds have hitherto been known to be used as absorbents for the
rays within the near infrared and infrared regions, but the cyanine
compounds are generally unstable to light and heat. On the other hand,
since naphthalocyanine compounds are extremely stable to light, heat and
humidity and excellent in toughness, they attract attention to be used as
polymer materials for preparing films or thin membranes having high
performance characteristics by blending with various dyes, pigments,
optical information recording media, photoelectric conversion media,
electron photographic sensors and polymer materials.
However, naphthalocyanine compounds are generally scarcely soluble in
organic solvents and thus difficulties are encountered in forming films
thereof by ordinary film forming processing. Accordingly, there is an
earnest demand for a compound having excellent properties comparable to
naphthalocyanine compounds and capable of forming a film, and there is
also an earnest demand for the development of a process for preparing such
a compound on an industrial scale.
Also already proposed and applied for practical use as optical recording
media are recording media each having an inorganic recording film layer
made of a low melting point metal such as Te, Te alloys or Bi alloys.
However, production efficiency of such a recording medium having an
inorganic recording film layer is low since the recording film layer must
be formed by vacuum evaporation, or sputtering and there is a problem in
recording density since the thermal conductivity of the recording film
layer is high. Furthermore, since a harmful metal is used to prepare a
recording medium having such an inorganic recording film layer, it is
essential to overcome the problems concerning operation environment and
waste water disposal.
In order to solve these problems, various proposals have been made to use
phthalocyanine pigments which are known as blue to green pigments and
excellent in stability as materials for optical recording media, specific
examples being copper phthalocyanine, lead phthalocyanine, titanium
phthalocyanine, vanadyl phthalocyanine and tin phthalocyanine (Unexamined
Japanese Patent Publication Nos. 36490/1983 and 11292/1984). However,
these pigments are inferior in matching with the semiconductor lasers,
which are commonly used as the recording lasers at the present day, having
oscillation wavelengths at approximately 780 to 830 nm, since they have
maximum absorption wavelengths in the vicinity of 700 nm.
Under these circumstances, although there is proposed a process in which
the absorption wavelengths are shifted to the long wavelenth region by
means of processing with organic solvents or heating treatment, such a
process has not yet been applied for practical use since these metal
phthalocyanine pigments are scarcely soluble in organic solvents, in
addition to complicated processing steps, so that it is impossible to form
a thin film on a substrate made of a thermoplastic resin substrate, such
as polycarbonate by coating solutions thereof and it is inevitable to use
vacuum evaporation coating or sputtering technique.
In order to solve various problems described above, an optical recording
medium has been proposed, in which a soluble organic pigment is used to
form a recording film layer on a substrate by coating. More specifically,
developed and applied for practical use is an optical recording medium
which is formed by spin coating an organic pigment which has an absorption
wavelength within the oscillation wavelengths of semiconductor lasers and
is soluble in organic solvents, more specific examples of such a pigment
being dithiol-metal complexes, polymethine pigments, squaraine pigments,
cyanine pigments and naphthoquinone pigments.
However, the optical recording media containing the aforementioned organic
pigments have disadvantages that they are poor in durability and
weather-proof properties and low in reflectivity needed for reproducing
the informations. Also known in the art as pigments which are excellent in
durability and weather-proof properties and have absorption peaks vicinal
to 800 nm are naphthalocyanines having the tetraazaporphyrin skeletal
structure similar to phthalocyanine pigments (Inorg. Chim. Acta., 44, L209
(1980); Zh. Obshch. Khim., 42(3), 696 (1972)). However, these known
naphthalocyanines and metal salts thereof have a disadvantage that they
are more scarcely soluble in general organic solvents than the
corresponding phthalocyanine compounds.
In recent years, various investigations have been made to improve the
solubility of naphthalocyanines and metal salts thereof in organic
solvents (Specification of U.S. Pat. No. 4,492,750, Specification of U.S.
Pat. No. 4,725,525, Unexamined Japanese Patent Publication No. 25886/1986,
J. Am. Chem. Soc., 106, 7404 (1984), Unexamined Japanese Patent
Publication No. 177287/1986, Unexamined Japanese Patent Publication No.
177288/1986 and Unexamined Japanese Patent Publication No. 184565/1985),
and it has been known that aromatic hydrocarbon solvents and halogenated
solvents may be used as the organic solvents for dissolving these
compounds. However, since the solubilities of these compounds, for
example, in saturated hydrocarbon solvents and alcohol solvents are
extremely low, there arises a problem that a layer resisting to solvent
must be formed on a polymethyl methacrylate or polycarbonate substrate
when a recording film layer is formed on such a substrate.
Further known to improve the general solubilities of naphthalocyanines is a
method in which plural substituting groups having long chain alkyl groups
are introduced. However, if the solubility is improved by such a method,
the melting point of the resultant product is lowered to induce a
disadvantage that the recording film layer tends to melt when the optical
recording medium is subjected to reproduction for a long time as well as
during the recording step. Accordingly, there is a demand for the
development of a method for solubilizing the naphthalocyanine compounds in
saturated hydrocarbon solvents and alcohol solvents without lowering the
melting points thereof.
In general, naphthalocyanines have a disadvantage that the once formed
amorphous recording film is crystallized gradually under a high
temperature and high humidity condition to lose the recorded information
since they have large planar .chi.-conjugated bonds to have extreme
association force between individual molecules. Accordingly, there arises
a problem that such crystallization must be suppressed.
Accordingly, an object of this invention is to provide a novel derivative
of naphthalocyanine containing a perfluoroalkyl group, which is excellent
in weatherability, high in solubility in various organic solvents and
capable of forming a film, and to provide a process for preparing the
same.
Another object of this invention is to provide an industrially useful
process for preparing a derivative of naphthalocyanine containing a
perfluoroalkyl group at high yield without using any special apparatus and
reaction catalyst within a short time.
A further object of this invention is to provide an optical recording
medium which has high sensitivity and durability including resistance to
reproducing laser beam, resistance to environment and resistance to
crystallization.
DISCLOSURE OF THE INVENTION
According to the present invention, there is provided a derivative of
naphthalocyanine containing a perfluoroalkyl group represented by the
following general formula (IV) of:
##STR1##
(wherein M stands for H.sub.2, copper, (R).sub.3 SiO--Si--OSi(R).sub.3 or
[F(CF.sub.2).sub.n.sbsb.5 --(R).sub.2 SiO--Si--OSi(R).sub.3 where R is an
alkyl group having 1 to 10 carbon atoms; n.sub.1, n.sub.2, n.sub.3 and
n.sub.4 each stand for an integer of from 0 to 2 and n.sub.5 stands for an
integer of 1 to 10; n.sub.1 +n.sub.2 +n.sub.3 +n.sub.4 .noteq. 0 when M is
H.sub.2, copper or (R).sub.3 SiO--Si--OSi(R).sub.3.
Meantime, both of the naphthalocyanine derivative containing a
perfluoroalkyl group represented by the general formula (IV) wherein M is
H.sub.2, and the naphthalocyanine derivative containing a perfluoroalkyl
group represented by the general formula (IV) wherein M are other than
H.sub.2 are novel compounds.
The present invention further provides an optical recording medium wherein
a recording film layer mainly composed of a naphthalocyanine derivative
containing a perfluoroalkyl group represented by the general formula (IV)
is formed on a substrate. It is preferred to use, as a main component of
the recording film layer, a single or mixed derivative of naphthalocyanine
containing a perfluoroalkyl group and represented by the aforementioned
general formula (IV) wherein M is other than H.sub.2 and copper or a
mixture of a single or mixed derivative of naphthalocyanine containing a
perfluoroalkyl group and represented by the formula (IV) wherein M is
other then H.sub.2 and copper with a single or mixed derivative of
naphthalocyanine containing a perfluoroalkyl group represented by the
aforementioned general formula (IV) wherein M is H.sub.2 or copper.
The present invention further provides a process for preparing a derivative
of naphthalocyanine containing a perfluoroalkyl group represented by the
aforementioned general formula (IV), comprising reacting a
naphthalocyanine with a perfluoroalkanoyl peroxide represented by the
following general formula (III) of:
##STR2##
(wherein n.sub.5 stands for an integer of from 1 to 10.)
BEST EMBODIMENT FOR THE PRACTICE OF THE INVENTION
The present invention will be described more in detail in the following
description.
The derivatives of naphthalocyanine containing a perfluoroalkyl group,
provided by this invention, is represented by the following general
formula (IV) of:
##STR3##
In the formula, M stands for H.sub.2, copper, (R).sub.3
SiO--Si--OSi(R).sub.3 or [F(CF.sub.2).sub.n.sbsb.5 (R).sub.2
SiO--Si--OSi(R).sub.3 where R is an alkyl group having 1 to 10 carbon
atoms; n.sub.1, n.sub.2, n.sub.3 and n.sub.4 each stand for an integer of
from 0 to 2 and n.sub.5 stands for an integer of 1 to 10; and n.sub.1
+n.sub.2 +n.sub.3 +n.sub.4 .noteq.0 when M is H.sub.2, copper or (R).sub.3
SiO--Si--OSi(R).sub.3. It becomes difficult to prepare the derivatives if
n.sub.5 is more than 10, either one of n.sub.1, n.sub.2, n.sub.3 and
n.sub.4 is more than 3 or R is an alkyl group having more than 11 carbon
atoms. Meantime, both of the naphthalocyanine derivative containing a
perfluoroalkyl group represented by the general formula (IV) wherein M is
H.sub.2 (hereinafter referred to as Naphthalocyanine Derivative A), and
the naphthalocyanine derivatives each containing a perfluoroalkyl group
represented by the general formula (IV) wherein M are other than H.sub.2
(hereinafter referred to as Naphthalocyanine Derivatives B) are novel
compounds.
It is preferred that the perfluoroalkylation ratio of the derivatives of
naphthalocyanine each containing a perfluoroalkyl group, according to this
invention, ranges from 100 to 800% for the aforementioned Naphthalocyanine
Derivative A and ranges from 100 to 900% for the aforementioned
Naphthalocyanine Derivatives B. When one perfluoroalkyl group is
introduced per one naphthalocyanine molecule, it will be described that
the perfluoroalkylation ratio is 100%.
Preferable derivatives of naphthalocyanine each containing a perfluoroalkyl
group and represented by the aforementioned general formula (IV) include
perfluoromethylated naphthalocyanine, perfluoroethylated naphthalocyanine,
perfluoropropylated naphthalocyanine, perfluorobutylated naphthalocyanine,
perfluoropentylated naphthalocyanine, perfluorohexylated naphthalocyanine,
perfluoroheptylated naphthalocyanine, perfluorooctylated naphthalocyanine,
perfluorononylated naphthalocyanine, perfluorodecylated naphthalocyanine,
tetraperfluoroethyl naphthalocyanine, tetraperfluoropropyl
naphthalocyanine, perfluoromethylated copper naphthalocyanine,
perfluoroethylated copper naphthalocyanine, perfluoropropylated copper
naphthalocyanine, perfluorobutylated copper naphthalocyanine,
perfluoropentylated copper naphthalocyanine, perfluorohexylated copper
naphthalocyanine, perfluoroheptylated copper naphthalocyanine,
perfluorooctylated copper naphthalocyanine, perfluorononylated copper
naphthalocyanine, perfluorodecylated copper naphthalocyanine,
tetraperfluorobutyl copper naphthalocyanine, diperfluoropentyl copper
naphthalocyanine, diperfluorohexyl copper naphthalocyanine,
diperfluoroheptyl copper naphthalocyanine, diperfluorooctyl copper
naphthalocyanine, diperfluorononyl copper naphthalocyanine,
diperfluorodecyl copper naphthalocyanine, pentafluoropropyl copper
naphthalocyanine, perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon
naphthalocyanine, perfluoropropylated
(perfluoropropyl-dihexylsiloxy-trihexylsiloxy-silicon) naphthalocyanine,
perfluoropropylated (perfluoropropyl-dihexylsiloxy-trihexylsiloxy-silicon)
naphthalocyanine, perfluoropropylated
(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon) naphthalocyanine,
perfluoropropylated
(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon) naphthalocyanine,
perfluoropropylated (perfluoropropyldiethylsiloxy-triethylsiloxy-silicon)
naphthalocyanine, tetraperfluoropropyl-bis(trimethylsiloxy) silicon
naphthalocyanine, diperfluoropropyl-bis(trimethylsiloxy) silicon
naphthalocyanine, diperfluorobutyl-bis(trimethylsiloxy) silicon
naphthalocyanine, diperfluoropentyl-bis(trimethylsiloxy) silicon
naphthalocyanine, diperfluorohexyl-bis(trimethylsiloxy) silicon
naphthalocyanine, diperfluoroheptyl-bis(trimethylsiloxy) silicon
naphthalocyanine, perfluorooctyl-bis(trimethylsiloxy) silicon
naphthalocyanine, perfluorononyl-bis(trimethylsiloxy) silicon
naphthalocyanine, perfluorodecyl-bis(trimethylsiloxy) silicon
naphthalocyanine, tetraperfluoroethyl-bis(triethylsiloxy) silicon
naphthalocyanine, tetraperfluoropropyl-bis(triethylsiloxy) silicon
naphthalocyanine, perfluoropropyl-bis(triethylsiloxy) silicon
naphthalocyanine, perfluorobutyl-bis(triethylsiloxy) silicon
naphthalocyanine, perfluoropentyl-bis(triethylsiloxy) silicon
naphthalocyanine, perfluorohexyl-bis(triethylsiloxy) silicon
naphthalocyanine, perfluoroheptyl-bis(triethylsiloxy) silicon
naphthalocyanine, diperfluoroethyl-bis(tripropylsiloxy) silicon
naphthalocyanine, perfluoropropyl-bis(tripropylsiloxy) silicon
naphthalocyanine, diperfluoropropyl-bis(tripropylsiloxy) silicon
naphthalocyanine, triperfluoropropyl-bis(tripropylsiloxy) silicon
naphthalocyanine, perfluorobutyl-bis(tripropylsiloxy) silicon
naphthalocyanine, perfluoroethyl-bis(tributylsiloxy) silicon
naphthalocyanine, diperfluoroethyl-bis(tributylsiloxy) silicon
naphthalocyanine, tetraperfluoroethyl-bis(tributylsiloxy) silicon
naphthalocyanine, perfluoropropyl-bis(tributylsiloxy) silicon
naphthalocyanine, diperfluoropropyl-bis(tributylsiloxy) silicon
naphthalocyanine, tetraperfluoropropyl-bis(tributylsiloxy) silicon
naphthalocyanine, perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon
naphthalocyanine,
diperfluoropropyl(perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon)
naphthalocyanine,
triperfluoropropyl(perfluoro-propyldipropylsiloxy-tripropylsiloxy-silicon)
naphthalocyanine,
diperfluoropropyl(perfluoropropyl-diethylsiloxy-triethylsiloxy-silicon)
naphthalocyanine,
perfluoropropyl(perfluoropropyldiethylsiloxy-triethylsiloxy-silicon)
naphthalocyanine, diperfluoroethyl-bis(trihexylsiloxy) silicon
naphthalocyanine, triperfluoroethyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluoropropyl-bis(trihexylsiloxy) silicon
naphthalocyanine, diperfluoropropyl-bis(trihexylsiloxy) silicon
naphthalocyanine, tetraperfluoropropyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluorohexyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluoromethyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluoroethyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluoropropyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluorobutyl-bis(trihexylsiloxy) silicon
naphthalocyanine, perfluoropentyl-bis(trihexylsiloxy) silicon
naphthalocyanine and perfluorohexyl-bis(trihexylsiloxy) silicon
naphthalocyanine. Meanwhile, in the illustrated derivatives of
naphthalocyanine each containing a perfluoroalkyl group,
"perfluoroalkylation" such as "perfluoropropylation" means that a
perfluoroalkyl group represented by [(CF.sub.2)n.sub.4.sbsb.5
F].sub.n.sbsb.4 (wherein n.sub.4 and n.sub.5 are the same as n.sub.4 and
n5 defined in the aforementioned general formula (IV) is coupled to at
least one of six positions of the naphthalene ring present in the
aforementioned general formula (IV) at which such a group may be coupled.
However, when M in the aforementioned general formula (II) is [F(CF.sub.2
--.sub.n.sbsb.5 (R).sub.2 SiO--Si--OSi(R).sub.3,it is not always essential
that a perfluoroalkyl group is coupled to the naphthalene ring since a
perfluoroalkyl group is already present in M.
The process for preparing a derivative of naphthalocyanine represented by
the aforementioned general formula (IV), according to this invention, is
characterized in that a particular perfluoroalkanoyl peroxide is reacted
with any of naphthalocyanines.
The perfluoroalkanoyl peroxides, which are used as a feed component in the
process of this invention, may be represented by the following general
formula (III) of:
##STR4##
In the formula set forth above, n.sub.5 stands for an integer of from 1 to
10. n.sub.5 must be within the range as defined above, since the
solubility of the peroxides in a solvent is lowered if n.sub.5 exceeds 10
so that handling thereof in reaction becomes difficult. Specific examples
of the perfluoroalkanoyl peroxides represented by the aforementioned
general formula (III) include bis(perfluoroacetyl) peroxide,
bis(perfluoropropionyl) peroxide, bis(perfluorobutyryl) peroxide,
bis(perfluoropentanoyl) peroxide, bis(perfluorohexanoyl) peroxide,
bis(perfluoroheptanoyl) peroxide, bis(perfluorooctanoyl) peroxide,
bis(perfluoropelargonyl) peroxide, bis(perfluorodecanoyl) peroxide and
bis(perfluoroundecanoyl) peroxide.
Specific examples of the naphthalocyanines which may be reacted with the
aforementioned perfluoroalkanoyl peroxides in the process of this
invention include naphthalocyanine, copper naphthalocyanines, and silicon
naphthalocyanines represented by the following general formula (VII) of:
##STR5##
(wherein R stands for an alkyl group having 1 to 10 carbon atoms.)
Specific examples of the silicon naphthalocyaines include
bis(trimethylsiloxy) silicon naphthalocyanine, bis(triethylsiloxy) silicon
naphthalocyanine, bis(tripropylsiloxy) silicon naphthalocyanine,
bis(tributylsiloxy) silicon naphthalocyanine, bis(tripentylsiloxy) silicon
naphthalocyanine, bis(trihexylsiloxy) silicon naphthalocyanine,
bis(triheptylsiloxy) silicon naphthalocyanine, bis(trioctylsiloxy) silicon
naphthalocyanine, bis(trinonylsiloxy) silicon naphthalocyanine and
bis(tridecylsiloxy) silicon naphthalocyanine.
It is preferred that the naphthalocyanines and the perfluoroalkanoyl
peroxides are charged in a molar ratio of from 1:0.2 to 20, particularly
1:0.5 to 10. If the molar ratio of charged perfluoroalkanoyl peroxide is
less than 0.2, the yield of the produced derivative of naphthalocyanine
containing an alkyl group is lowered and the ratio of perfluoroalkyl group
introduced in the produced naphthalocyanine is reduced, whereas it is not
preferable that the ratio of charged perfluoroalkanoyl peroxide exceeds
20, since sole decomposition of perfluoroalkanoyl peroxide becomes
predominant to make the process impertinent for industrial preparation
process.
The reaction between the perfluoroalkanoyl peroxides and the
naphthalocyanines may proceed under atmospheric pressure, preferably at a
reaction temperature of from -20.degree. to 150.degree. C., particularly
preferably from 0.degree. to 100.degree. C., for 0.5 to 20 hours, whereby
derivatives of naphthalocyanine each containing an introduced
perfluoroalkyl group, such as CF.sub.3 --, F(CF.sub.2 --.sub.2, F(CF.sub.2
--.sub.3, F(CF.sub.2 --.sub.4, F(CF.sub.2 --.sub.5, F(CF.sub.2 --.sub.6,
F(CF.sub.2 --.sub.7, F(CF.sub.2 --.sub.8, F(CF.sub.2 --.sub.9, and
F(CF.sub.2 --.sub.10, , may be prepared. The reaction time becomes too
long if the reaction temperature is lower than -20.degree. C., whereas the
pressure during reaction becomes disadvantageously high to arise
difficulty in reaction operation if the reaction temperature is higher
than 150.degree. C.
When the perfluoroalkanoyl peroxides are reacted with the naphthalocyanines
according to this invention, the reaction may proceed in the presence of a
solvent, for example a halogenated aliphatic compound, for easy handling
of the perfuloroalkanoyl peroxide. The most preferable halogenated
aliphatic solvent from the industrial point of view is
1,1,2-trichloro-1,2,2-trifluoroethane.
The reaction products prepared by this invention may be purified through
known processes including column chromatography.
The optical recording medium of this invention is characterized in that the
main component of the recording film layer formed on a substrate is any of
the derivatives of naphthalocyaines (hereinafter referred to as
Naphthalocyanine Derivatives C) represented by the aforementioned general
formula (IV), more preferably the main component is selected from the
derivatives of naphthalocyanines (hereinafter referred to as
Naphthalocyanine Derivatives D) included in the Naphthalocyanine
Derivatives C wherein M in the formula is other than H.sub.2 and copper,
or a mixture of the Naphthalocyanine Derivatives D with any of the
derivatives of naphthalocyanine (hereinafter referred to as
Naphthalocyanine Derivatives E) wherein M in the formula is H.sub.2 or
copper.
Since each of the derivatives of naphthalocyanine according to this
invention has perfluoroalkyl group, the association power between
individual molecules is lowered, as compared to the unsubstituted
naphthalocyanine, so that the solubility thereof in a solvent is
remarkably improved. Meanwhile, although the solubility may be improved by
the introduction of an alkyl group into naphthalocyanine, improvement in
solubility is appreciably improved by the introduction of a perfluoroalkyl
group when the product prepared by the introduction of a perfluoroalkyl
group having a certain number of carbon atom is compared to the product
prepared by the introduction of an alkyl group having the same number of
carbon atoms. In general, the melting points of naphthalocyanines are
lowered gradually with the increase in number of the introduced
substituting groups and as described above, since the products prepared by
the introduction of perfluoroalkyl groups have the solubilities equivalent
to or higher than the solubilities of the products prepared by the
introduction of alkyl groups even when the number of introduced
substituting groups is smaller, the aforementioned derivatives of
naphthalocyanine are compounds which are improved in solubility and
suppressed in attendant lowering of melting point. Particularly, since the
aforementioned Naphthalocyanine Derivatives D are introduced with
perfluoroalkyl groups which are intensive in steric repelling force, they
are particularly preferable for use as the main component in the recording
film layer without appreciable reduction in reflectivity due to
intermolecular association. On the other hand, the aforementioned
Naphthalocyanine Derivatives E have the tendency that the reflectivities
and the absorbancies (100 -- Reflectivity -- Percent Transmission) thereof
are lower as compared to those of the aforementioned Naphthalocyanine
Derivatives D, so that the stability against the reproducing laser beam
can be improved by using a mixture of the Naphthalocyanine Derivatives D
with the Naphthalocyanine Derivatives E as the main component for forming
the recording film layer by the utilization of the aformentioned
characteristics. It is preferable that the mixing ratio of the
aforementioned Naphthalocyanine Derivatives D and the Naphthalocyanine
Derivatives E ranges within 10:1 to 5 by weight, particularly preferably
within 10:1 to 3 by weight. Meantime, preferable examples of the
aforementioned derivatives of naphthalocyanine include those specifically
represented by the general formula (IV) set forth above, and in principle
they may be used singly or in the form of a mixture.
In order to form a recording film layer on a substrate to prepare an
optical recording medium in the present invention, the aforementioned
derivatives of naphthalocyanine may be dissolved, for example, in an
appropriate organic solvent and coated by spray coating, spin coating or
other processes to be carried on the substrate. Suitable materials for the
substrate include thermoplastic resins such as polyvinyl chloride resins,
acrylic resins, polyolefin resins, polycarbonate resin and polyvinyl
acetal resin; thermosetting resins such as epoxy resins, unsaturated
polyester resins and vinyl ester resins; and glass and metals. For
instance, when recording and reproduction are effected by irradiating a
laser beam from the substrate side, the substrate must be transparent in
the wavelength range of the used laser beam. The substrate may have a
construction composed of a flat plate molded from the aforementioned
materials and a photocured resin layer laminated on the flat plate, the
photocured resin layer having a surface on which a guide track pattern is
transferred.
For instance, when the material for the substrate is a thermoplastic resin,
a solvent which does not damage the pre-groove or pre-pit formed in the
substrate may be used for forming the aforementioned recording film layer,
the examples being saturated hydrocarbon solvents such as pentane, hexane,
heptane, octane, nonane, decane, cyclopentane, cyclohexane and
cycloheptane; alcohol solvents such as methanol, ethanol, propanol,
isopropyl alcohol, butanol, isobutyl alcohol and t-butyl alcohol; benzene,
toluene, xylene, chlorobenzene, 1-chloronaphthalene, methylene chloride,
chloroform, carbon tetrachloride, trichloroethane, diethyl ether,
ethyleneglycol dimethyl ether, diethyleneglycol monomethyl ether,
diethyleneglycol dimethyl ether, ethylbenzene, methyl ethyl ketone,
acetone, methyl propyl ketone, cyclopentanone, cyclohexanone, acetone
alcohol, diacetone alcohol, diisobutyl ketone, propylene oxide, furan,
1,3-dioxolan, acetate, dimethoxymethane, dimethoxypropane,
diethoxymethane, 1,2-dimethoxypropane, 2,2-dimethoxypropane. 2-pentanone,
3-pentanone, 1,2-butylene oxide, n-butyl-2,3-epoxy propyl ether, carbon
disulfide, diisopropyl ether, nitromethane, acetonitrile,
1,3-dicyanopropane, dioxane and ethyl acetate. These solvents may be used
singly or in the form of a mixture.
The aforementioned recording film layer may be formed by applying each of
the aforementioned derivatives of naphthalocyanine used as the main
component of the recording film layer in the laminated structure or in the
single layer structure. The aforementioned derivatives of naphthalocyanine
may be used singly or in the form of a mixture, and each of them may be
laminated or they may be mixed together and then used to form a single
layer structure. The film thickness of the aforementioned recording film
layer ranges preferably from 50 to 10000 .ANG., particularly preferably
from 100 to 5000 .ANG..
A reflected light may be used for the optical reproduction of the recorded
image stored in the aforementioned recording film layer. In order to raise
the contrast in this step, a metal layer having a high reflectivity may be
provided, if necessary, on the surface of the recording film layer
opposite to the substrate when the image is written in and read out from
the substrate side; or a metal layer having a high reflectivity may be
provided between the substrate and the recording film layer when the image
is written in and read out from the side opposite to the substrate, namely
from the recording film layer side. As the metal having a high
reflectivity, Al, Cr, Au, Pt and Sn may be used. Such a layer may be
formed by the known thin film forming processes, such as vacuum
evaporation, sputtering or plasma deposition, and the thickness thereof
ranges preferably from 100 to 10000 .ANG..
In order to improve the smoothness of the surface of the aforementioned
substrate, a uniform membrane of an organic polymer compound may be
provided over the substrate. Commercially available polymers, such as
polyesters or polyvinyl chloride, may be used as the organic polymer
compound.
Furthermore, in order to improve the stability and protection properties of
the recording film layer and further to lower the surface reflectivity to
increase the sensitivity, a protection layer may be provided as an
outermost ply of the recording film layer. Materials for forming such a
protection layer include polyvinilidene chloride, polyvinyl chloride,
copolymers of vinylidene chloride and acrylonitrile, polyvinyl acetate,
polyimide, polymethyl methacrylate, polystyrene, polyisoprene,
polybutadiene, polyurethane, polyvinyl butyral, fluorinated rubbers,
polyesters, epoxy resins, silicone resins and cellulose acetate, these
materials being used singly or in the form of a mixture. With the aim to
reinforce the properties of such a protection layer, silicone oil, an
antistatic agent or a cross-linking agent may be present in the layer, or
plural protection layers may be provided. Such a protection layer may be
formed, for example, by dissolving a material for forming the protection
layer followed by coating, or by laminating a thin film for forming the
protection layer. The thickness of the protection layer ranges preferably
from 0.1 to 10 .mu.m, particularly preferably from 0.1 to 2 .mu.m.
The derivatives of naphthalocyanine each containing a perfluoroalkyl group,
according to this invention, are novel compounds and are soluble in
various organic solvents, so that they are useful as optical information
recording media, photo-electric convertors, photosensitive materials for
electron photography or polymer materials for blending with other polymers
to form films or thin membranes having high performance characteristics.
Since particular perfluoroalkanoyl peroxides are used in the process of
this invention, perfluoroalkyl groups can be directly and easily
introduced into naphthalocyanines within a short period at high yield. In
addition, since no reaction catalyst and no special device are used, it is
extremely useful from the industrial standpoint of view.
Furthermore, since the optical recording medium according to this invention
is formed by using, as the main component for forming the recording film
layer, a compound excellent in resistance to laser beam used for
reproduction, resistance to environment and resistance to crystallization
and improved in solubility, it is high in sensitivity and excellent in
durability and thus extremely useful when used, for example, as an optical
disc, optical card or optical floppy.
EXAMPLES:
The present invention will be described more in detail by referring to
Examples and Test Examples thereof in the following description, but it is
to be noted here that the present invention is not restricted thereby.
EXAMPLE 1
0.5 g (0.7 mmol) of naphthalocyanine was added to and mixed with 10 g of
1,1,2-trichloro-1,2,2-trifluoroethane, to which added was 20 g of a
solution of 1,1,2-trichloro-1,2,2-trifluoroethane containing 3.5 mmol of
bis(perfluorobutyryl) peroxide to proceed the reaction at 40.degree. C.
for 5 hours. After the completion of reaction, 50 ml of chloroform was
added to the reaction mixture, which was then filtered to remove unreacted
materials. Then, the obtained chloroform layer was dried by using
magnesium sulfate, and the product was purified through column
chromatography. As a result, tetraperfluoropropyl naphthalocyanine
represented by the following structural formula was obtained at a yield of
72%.
##STR6##
Meanwhile, the number of perfluoropropyl groups introduced in
naphthalocyanine, i.e. the perfluoropropylation ratio, was determined by
.sup.19 F--NMR while using benzotrifluoride as an internal standard
indicator to find that the perfluoropropylation ratio was 400%, namely
four perfluoropropyl groups were introduced per one molecule. The UV
spectrum (Solvent used in Measurement: Chloroform), IR spectrum and
.sup.19 F-NMR spectrum of the thus prepared perfluoropropylated
naphtalocyanine are set forth below.
UV (nm): 261, 711.0, 729.0, 762.5.
IR (cm .sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.02 H) .delta.: -8 to
-10 (CF.sub.3), -20 to -38 (CF.sub.2), -46 to -58 (CF.sub.2).
EXAMPLE 2
Similar reaction and analyses were repeated as in Example 1, except that
the charged quantity of bis(perfluorobutyryl) peroxide was changed to 2.8
mmol, to prepare perfluoropropylated naphthalocyanine at a yield of 69%.
Meanwhile, the perfluoropropylation ratio was determined similarly to
Example 1 to find that the perfluoropropylation ratio was 300%. The
results of analyses of the thus prepared perfluoropropylated
naphthalocyanine are set forth below.
UV (nm): 260, 592.5, 649.5, 669.0, 726.5.
IR (cm .sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -8 to
-10 (CF.sub.3), -20 to -38 (CF.sub.2), -46 to -58 (CF.sub.2).
EXAMPLE 3
Similar reaction and analyses were repeated as in Example 1, except that
bis(perfluoropropionyl) peroxide was used in place of
bis(perfluorobutyryl) peroxide, to prepare perfluoroethylated
naphthalocyanine at a yield of 70%. Meanwhile, the perfluoroethylation
ratio was determined similarly to Example 1 to find that the
perfluoroethylation ratio was 400%. The results of analyses of the thus
prepared perfluoroethylated naphthalocyanine are set forth below.
UV (nm): 670.0, 735.5.
IR (cm .sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -8 to
-10 (CF.sub.3), -43 to -56 (CF.sub.2).
EXAMPLE 4
Similar reaction and analyses were repeated as in Example 1, except that
bis(perfluoroheptanoyl) peroxide was used in place of
bis(perfluorobutyryl) peroxide, to prepare perfluorohexylated
naphthalocyanine at a yield of 65%. Meanwhile, the perfluorohexylation
ratio was determined similarly to Example 1 to find that the
perfluorohexylation ratio was 400%.
The results of analyses of the thus prepared perfluorohexylated
naphthalocyanine are set forth below.
UV (nm): 260, 590.0, 670.8, 735.5.
IR (cm .sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -5 to
-10 (3F), -30.1 to -51.5 (10F).
EXAMPLE 5
Similar reaction and analyses were repeated as in Example 1, except that
bis(perfluorooctanoyl) peroxide was used in place of bis(perfluorobutyryl)
peroxide, to prepare perfluoroheptylated naphthalocyanine at a yield of
65%. Meanwhile, the perfluoroheptylation ratio was determined similarly to
Example 1 to find that the perfluoroheptylation ratio was 400%.
The results of analyses of the thus prepared perfluoroheptylated
naphthalocyanine are set forth below.
UV (nm): 261, 670.8, 735.5.
IR (cm.sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.:
-5 to -10(3F), -30.1 to -51.5(12F).
Example 6
Similar reaction and analyses were repeated as in Example 1, except that
0.2 g (0.26 mmol) of copper naphthalocyanine was used in place of
naphthalocyanine and that the charged quantity of bis(perfluorobutyryl)
peroxide was changed to 2.06 mmol, to prepare perfluoropropylated copper
naphthalocyanine at a yield of 36%. Meanwhile, the perfluoropropylation
ratio was determined similarly to Example 1 to find that the
perfluoropropylation ratio was 490%. The results of analyses of the thus
prepared perfluoropropylated copper naphthalocyanine are set forth below.
##STR7##
UV (nm): 668.5, 736.5.
IR (cm .sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -8 to
-10 (CF.sub.3), -20 to -38 (CF.sub.2). -46 to -58 (CF.sub.2).
EXAMPLE 7
Similar reaction and analyses were repeated as in Example 1, except that
0.5 g (0.37 mmol) of bis(trihexylsiloxy) silicon naphthalocyanine was used
in place of naphthalocyanine and that the charged quantity of
bis(perfluorobutyryl) peroxide was changed to 0.37 mmol, to prepare
(perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon) naphthalocyanine
having the structure as set forth below at a yield of 46%.
##STR8##
Meanwhile, the perfluoropropylation ratio was determined similarly to
Example 1 to find that the perfluoropropylation ratio was 100%. The
results of analyses and the melting point (mp) of the thus prepared
perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon naphthalocyanine are
set forth below.
UV (nm): 779, 761
IR (cm.sup.-1): 1340 (CF.sub.3 ), 1225 (CF.sub.2).
mp: 226.degree. C. to 228.degree. C. .sup.19 F--NMR (CDCl.sub.3, external,
CF.sub.3 CO.sub.2 H) .delta.: -2.8 (CF.sub.3), -18.0 (CF.sub.2), -45.7
(CF.sub.2).
EXAMPLE 8
Similar reaction and analyses were repeated as in Example 1, except that
0.5 g (0.37 mmol) of bis(trihexylsiloxy) silicon naphthalocyanine was used
in place of naphthalocyanine and that the charged quantity of
bis(perfluorobutyryl) peroxide was changed to 1.42 mmol, to prepare
diperfluoropropyl(perfluoropropyldihexhlsiloxy-trihexylsiloxy-silicon)
naphthalocyanine having the structure as set forth below at a yield of
46%.
##STR9##
Meanwhile, the perfluoropropylation ratio was determined similarly to
Example 1 to find that the perfluoropropylation ratio was 300%. The
results of analyses of the thus prepared
diperfluoropropyl(perfluoropropyldihexylsiloxy-trihexylsiloxy-silicon)
naphthalocyanine are set forth below.
UV (nm): 771.
IR (cm.sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -2.5 to
-5.5 (CF.sub.3), -17.0 to -21.5 (CF2), -44.5 to -46.8 (CF.sub.2).
EXAMPLE 9
Similar reaction and analyses were repeated as in Example 1, except that
0.5 g (0.46 mmol) of bis(tripropylsiloxy) silicon naphthalocyanine was
used in place of naphthalocyanine and that the charged quantity of
bis(perfluorobutyryl) peroxide was changed to 0.92 mmol, to prepare
diperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)
naphthalocyanine having the structure as set forth below at a yield of
13%.
##STR10##
Meanwhile, the perfluoropropylation ratio was determined similarly to
Example 1 to find that the perfluoropropylation ratio was 300%. The
results of analyses of the thus prepared
diperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)
naphthalocyanine are set forth below.
UV (nm): 764, 675.
IR (cm.sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -2.8 to
-6.0 (CF.sub.3), -17.2 to -19.0 (CF.sub.2), -44.0 to -47.9 (CF.sub.2).
EXAMPLE 10
Similar reaction and analyses were repeated as in Example 1, except that
0.5 g (0.46 mmol) of bis(tripropylsiloxy) silicon naphthalocyanine was
used in place of naphthalocyanine and that the charged quantity of
bis(perfluorobutyryl) peroxide was changed to 1.84 mmol, to prepare
triperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)
naphthalocyanine having the structure as set forth below at a yield of
50%.
##STR11##
Meanwhile, the perfluoropropylation ratio was determined similarly to
Example 1 to find that the perfluoropropylation ratio was 400%. The
results of analyses of the thus prepared
triperfluoropropyl(perfluoropropyldipropylsiloxy-tripropylsiloxy-silicon)
naphthalocyanine are set forth below.
UV (nm): 773, 668, 613.
IR (cm.sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -2.8 to
-6.5 (CF.sub.3), -17.5 to -22.0 (CF.sub.2), -45.0 to -52.0 (CF.sub.2).
EXAMPLE 11
Similar reaction and analyses were repeated as in Example 1, except that
0.5 g (0.50 mmol) of bis(triethylsiloxy)silicon naphthalocyanine was used
in place of naphthalocyanine and that the charged quantity of
bis(perfluorobutyryl) peroxide was changed to 1.00 mmol, to prepare
diperfluoropropyl(perfluoropropyldiethylsiloxy-triethylsiloxy-silicon)
naphthalocyanine having the structure as set forth below at a yield of
13%.
##STR12##
Meanwhile, the perfluoropropylation ratio was determined similarly to
Example 1 to find that the perfluoropropylation ratio was 300%. The
results of analyses of the thus prepared
diperfluoropropyl(perfluoropropyldietylsiloxy-triethylsiloxy-silicon)
naphthalocyanine are set forth below.
UV (nm): 767, 676.
IR (cm.sup.-1): 1340 (CF.sub.3), 1225 (CF.sub.2).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -2.8 to
-3.6 (CF.sub.3), -18.2 to -20.5 (CF2), -45.1 to -47.3 (CF.sub.2).
EXAMPLE 12
0.5 g (0.37 mmol) of bis(trihexylsiloxy)silicon naphthalocyanine was added
to and mixed with 20 ml of chloroform, to which added was 3.2 g of a
solution of 1,1,2-trichloro-1,2,2-trifluoroethane containing 0.16 g (0.37
mmol) of bis(perfluorobutyryl) peroxide to proceed the reaction at
40.degree. C. for 5 hours. After the completion of reaction, the reaction
mixture was rinsed with a 0.5 wt % aqueous solution of sodium hydroxide
and saturated aqueous saline. Then, the thus obtained chloroform layer was
dried with magnesium sulfate, and the product was purified through column
chromatography and further recrystallized by using a mixed solution of
hexane ethanol. As a result, perfluoropropyl-bis(trihexylsiloxy) silicon
naphthalocyanine represented by the following structural formula was
prepared at a yield of 43%.
##STR13##
Meanwhile, the number of perfluoroalkyl groups introduced in the
naphthalocyanine was determined by .sup.19 F--NMR while using
o-chlorobenzotrifluoride as an internal standard liquid to find that the
number of perfluoroalkyl groups was 1. The UV (Solvent Used in
Measurement: Chloroform), IR, .sup.1 H--NMR, .sup.19 F--NMR and the
melting point of the thus prepared perfluoropropyl-bis(trihexylsiloxy)
silicon naphtalocyanine are shown below.
UV (nm): 781, 766.
IR (cm.sup.-1) 1350 (CF.sub.3), 1225 (CF.sub.2).
.sup.1 H--NMR (CDCl.sub.3).delta.: 10.55 to 9.95 (m, 7H) 9.15 to 8.45 (m,
8H) 7.95 (b, 8H), 1.00 to 0.00 (m, 54H) -0.95 (b, 12H), -1.90 to -2.25 (m,
12H).
.sup.19 F--NMR (CDCl.sub.3, external, CF.sub.3 CO.sub.2 H) .delta.: -2.8
(CF.sub.3), -18.0 (CF.sub.2), -45.7 (CF.sub.2).
Melting Point (.degree.C.): 226 to 228.
TEST EXAMPLE 1
Perfluoroalkylated naphthalocyanines prepared by Examples 1 to 12 were
mixed with respective solvents as set forth in Table 1 to investigate the
solubilities thereof. The solubility of naphthalocyanine was investigated
as Comparative Example 1. The results are shown in Table 1.
TABLE 1
______________________________________
Example No./Solvent
a b c d e f g h i j
______________________________________
Example 1 .circleincircle.
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X .largecircle.
.DELTA.
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.DELTA.
X
Example 2 .circleincircle.
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X .largecircle.
.DELTA.
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.DELTA.
X
Example 3 .circleincircle.
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X .largecircle.
.DELTA.
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.DELTA.
X
Example 4 .circleincircle.
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X .largecircle.
X .circleincircle.
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X X
Example 5 .circleincircle.
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X .largecircle.
X .circleincircle.
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X X
Example 6 .circleincircle.
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X .largecircle.
X .circleincircle.
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X X
Example 7 .circleincircle.
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X .largecircle.
.DELTA.
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.DELTA.
.largecircle.
Example 8 .circleincircle.
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X .largecircle.
.DELTA.
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.largecircle.
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Example 9 .circleincircle.
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Example 10 .circleincircle.
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Example 11 .circleincircle.
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Example 12 .circleincircle.
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X .largecircle.
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.DELTA.
.DELTA.
Comparative X X X X X X X X X X
Example 1
______________________________________
The marks in the Table indicate the following meanings.
a: chloroform, b: Diethyl Ether, c: Tetrahydrofuran
d: Methanol, e: Benzene, f: Hexane, g: Ethyl Acetate
h: Acetone, i: Dimethylformamide, j: Ethanol
.circleincircle.: Easily Soluble, .largecircle.: Soluble .DELTA.: Scarcel
Soluble
X: Insoluble
As seen from the results set forth in Table 1, the derivatives of
naphthalocyanine each containing a perfluoroalkyl group, according to this
invention, are soluble in various solvents and thus useful for forming a
processed film.
EXAMPLES 13 to 15
Similarly to the preceding Examples,
triperfluoropropyl-bis(tripropylsiloxy) silicon naphthalocyanine (Example
13), diperfluoropropyl-bis(tributylsiloxy) silicon naphthalocyanine
(Example 14) and diperfluoroethyl-bis(tributylsiloxy) silicon
naphthalocyanine (Example 15) were synthesized and subjected to various
analyses to identify the structures thereof.
EXAMPLE 16
On each of the substrates having different compositions as set forth in
Table 2 and each having a thickness of 1.2 mm and a diameter of 130 mm,
coated by spin coating process was a solution consisting of 1 part by
weight of each of the derivatives of naphthalocyanine as set forth in
Table 2 and 99 parts by weight of a solvent, whereby each of recording
film layers was formed. The thickness of the thus formed recording film
layer was measured by "Dektak 3030" (Trade Name) produced by Sloan Co. The
thus prepared optical recording medium was placed on a turn table and
rotated at 1800 rpm, and pulse signals of 3.7 MHz were recorded thereon
within the radius range of from 40 to 60 mm by using an optical head
provided with a semiconductor laser having an oscillation wavelength of
830 nm with an output of 6 mW on the surface of the substrate so that the
laser beam is focused through the substrate on the recording film layer
from the substrate side. Then, using a similar device, the output of a
semiconductor laser on the surface of the substrate was set to 1.0 mW to
reproduce the recorded signals, and the CN ratio (carrier-noise ratio) at
the reproduction step was appraised. Furthermore, each of the prepared
optical recording media was allowed to stand under a high temperature and
high humidity condition (80.degree. C., 90% RH) for 3000 hours, and then
the CN ratio was measured. The results are shown in Table 2.
TABLE 2
__________________________________________________________________________
Derivative of Thickness
Initial
CN Ratio after the
Naphthalocyanine of film
CN Ratio
Lapse of 3000 hours
(ratio by weight)
Substrate*
Solvent
(.ANG.)
(dB) (dB)
__________________________________________________________________________
Example 12
PC Cyclohexane
700 62 62
Example 8
PC Cyclohexane
790 59 60
Example 9
PC Cyclohexane
760 62 60
Example 10
PC Cyclohexane
800 58 58
Example 11
PC Cyclohexane
830 57 59
Example 13
PMMA2P
Toluene
900 59 59
Exampl4 14
PMMA2P
Toluene
920 62 60
Example 15
PC Ethanol
680 60 61
Example 12
PC Ethanol
700 61 61
Example 8
PMMA Ethanol
720 58 58
Example 9
PMMA2P
Chloroform
910 57 58
Example 11
PMMA2P
Chloroform
890 59 57
Ex. 8:Ex. 1 (7:3)
PC Cyclohexane
1010 59 61
Ex. 15:Ex. 1 (9:2)
PC Cyclohexane
970 58 60
Ex. 15:Ex. 1 (8:2)
PC Cyclohexane
950 61 60
Ex. 15:Ex. 1 (7:3)
PC Cyclohexane
990 62 61
__________________________________________________________________________
*PC: Polycarbonate Substrate, PMMA: Polymethyl Methacrylate Substrate
PMMA2P: Polymethyl Methacrylate 2P Substrate
As will be seen from the results shown in Table 2, the derivatives of
naphthalocyanine used to form optical recording media, according to this
invention, form recording film layers having superior recording and
reproducing properties on various substrates, such as polycarbonate
substrate, and that the thus formed recording film layers are excellent in
amorphous film retention capability under an accelerated environmental
test condition.
COMPARATIVE EXAMPLE 2
A recording film layer was formed by coating, by the spin coating process
similar to Example 16, a solution consisting of 1 part by weight of a
compound represented by the following structural formula and 99 parts by
weight of toluene on a polymethyl methacrylate 2P substrate having a
thickness of 1.2 mm and a diameter of 130 mm. The thickness of the thus
formed recording film layer was 1000 .ANG.. Similarly to Example 16,
recording and reproduction were effected using the thus prepared recording
medium to find that the CN ratio was 39 dB and that the recording and
read-out of the signals were not so satisfactory. In addition, the
recording film layer was crystallized to form microcrystals to lose its
reproduction capability after it was retained under a high temperature and
high humidity condition (80.degree. C., 90% RH) for 500 hours.
##STR14##
COMPARATIVE EXAMPLE 3
A recording film layer was formed by coating, by the spin coating process
similar to Example 16, a solution consisting of 1 part by weight of a
cyanine pigment NK-2905 (produced by Nippon Kanko Shikiso Kenkyusho) and
99 parts by weight of dichloroethane on a polymethyl methacrylate 2P
substrate having a thickness of 1.2 mm and a diameter of 130 mm. The
thickness of the thus formed recording film layer was 700 .ANG.. The thus
prepared recording medium was allowed to stand for 3000 hours under a high
temperature and high humidity condition (80.degree. C., 90% RH), and then
the reflectivity thereof was measured to find that the reflectivity was
abruptly lowered after the lapse of about 500 hours to show the lack of
satisfactory durability. The CN ratio retention properties under an
accelerated environmental condition was appraised by a similar procedure
as described in Example 16 to find that the CN ratio was lowered to 70% of
the initial CN ratio.
EXAMPLE 17
Durability to a reproducing laser beam (830 nm) of each of the optical
recording media prepared in Example 16 was appraised. The appraisal test
was conducted by measuring the CN ratio after repeated reproduction of
10.sup.6 times while setting the output of the used reproducing laser beam
to 1.0 mW, 1.4 mW and 1.6 mW. The results are shown in Table 3.
TABLE 3
______________________________________
Derivative CN Ratio after Repeated
of Naphtha-
Initial Reproduction of 10.sup.6 Times
locyanine CN Ratio (dB)
(ratio by wt.)
(dB) 1.0 mW 1.4 mW 1.6 mW
______________________________________
Example 12 62 62 62 52
Example 8 59 59 58 50
Example 9 62 62 60 50
Example 10 58 58 58 43
Example 11 57 57 57 42
Example 13 59 59 59 42
Example 14 62 62 62 46
Example 15 60 60 60 48
Example 12 61 61 60 44
Example 8 58 58 58 41
Example 9 57 57 57 40
Example 11 59 59 57 38
Ex. 8:Ex. 1 (7:3)
59 59 59 54
Ex. 15:Ex. 1 (8:2)
58 58 57 52
Ex. 15:Ex. 1 (8:2)
61 61 61 52
Ex. 15:Ex. 1 (7:3)
62 62 62 51
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As will be seen from the results set forth in Table 3, it was found that
the derivatives of naphthalocyanine used in the present invention could
retain the initial CN ratios after the repeated reproduction of 10.sup.6
times at 1.4 mW, although the CN ratios were gradually lowered when an
extremely intensive reproducing beam of 1.6 mW was used.
COMPARATIVE EXAMPLE 4
The durability to reproducing laser beams of the optical recording medium
prepared by Comparative Example 2 was appraised similarly to Example 17.
The result revealed that the CN ratio began to lower after the repeated
reproduction of 10.sup.4 times when a reproducing laser beam of 1.0 mW was
used and tracking cound not be traced after the repeated reproduction of
10.sup.5 times.
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